Dioxetanes decomposition

Yields of excited states from 1,2-dioxetane decomposition have been determined by two methods. Using a photochemical method (17,18) excited acetone from TMD is trapped with /n j -l,2-dicyanoethylene (DCE). Triplet acetone gives i7j -l,2-dicyanoethylene with DCE, whereas singlet acetone gives 2,2-dimethyl-3,4-dicyanooxetane. By measuring the yields of these two products the yields of the two acetone excited states could be determined. The yields of triplet ketone (6) from dioxetanes are determined with a similar technique. 

A dramatic solvent effect in the thermolysis of tetramethyldioxetane, which followed the isokinetic relationship A/7 = /3A5 for a variety of solvents, formed the basis for the postulation of the concerted mechanism. However, it was shortly thereafter reported that the dramatic solvent effect in methanol was the result of catalysis by transition-metal ion impurities. In the presence of metal-ion complexing agents such as EDTA or Chelex 100, the menacing catalysis could be suppressed. That utmost care must be taken in measuring reliable kinetic parameters in 1,2-dioxetane decomposition cannot be overemphasized. 

Dioxetane decomposition has also been proposed to account for chemiluminescence from other reactions (43), including gas-phase reactions of singlet oxygen with ethylene and vinyl ethers (53). 

McCapra, F. (1977). Alternative mechanism for dioxetane decomposition. Chem. Commun., pp. 946-948. 

Me Capra in particular proposed n> that the chemiluminescence reactions of a large number of organic compounds had this concerted dioxetane decomposition step as key reaction in the production of electronically excited products, namely acridinium salts 25,26,27) indolylperoxides 28>, activated oxalic esters 29>, diphenyl carbene 30>, tetrakis-dimethylamino-ethylene 31 32>, lucigenin 33>, and substituted imidazoles 23>. 

For other photochemical reaction products from dioxetane decomposition, see Section X.). 

It was pointed out that these values are only approximate but they nevertheless demonstrate the high exergonicity of dioxetane decomposition. The sft2 carbons in the dioxetanones and -diones appear to stabilize the 4-membered ring peroxide. 

The contemporary trends of dioxetane chemistry include a number of fundamental and applied aspects. The fundamental aspects encompass the stereoselective synthesis and the transformations of novel chiral dioxetanes, as well as the mechanistic studies on the thermal, electron-transfer-induced and catalytic dioxetane decomposition. The emphasis lies on the elucidation of the excited-state generation in these chemiluminescent processes. 

A wealth of experimental data on the thermal dioxetane decomposition and the excited-state generation in the thermolysis process has been comprehensively surveyed in previous reviews". During the last decade, computational elucidation of the thermal cleavage received major attention and in the present subsection we consider the relevant smd-ies. Computations on the dioxetane thermolysis were conducted by both ab initio and semiempiricaP methods at different levels of sophistication. 

To assess the role of electron transfer in the dioxetane decomposition, a comparison of the reaction pathways for the neutral dioxetane and its negatively charged ion is relevant (cf. Figure 1). The energy profiles for the cleavage of a 1,2-dioxetane and its 1,2- dioxetane radical anion as a function of stretching the 0-0 bond, as calculated by the PM3 method. 

Phosphorescence emission from triplet states of carbonyl compounds formed through dioxetane decomposition can only be observed under specific conditions in the absence... 

Two extreme mechanisms have been proposed for the unimolecular dioxetane decomposition the concerted mechanism , whereby cleavage of the peroxide and the ring C—C bond occurs simultaneously, and the biradical mechanism whereby the initial cleavage of the 0—0 bond leads to the formation of a 1,4-dioxy biradical whose subsequent C—C bond cleavage leads to the formation of the two carbonyl fragments (Scheme 8). Although the biradical mechanism adequately explains the activation parameters obtained for most of the dioxetanes smdied, it appears not to be the appropriate mechanistic model for the rationalization of singlet and triplet quanmm yields. Therefore, an intermediate mechanism has been proposed, whereby the C—C and 0—0 bonds cleave in a concerted, but not simultaneous, manner (Scheme 8) . 

Ruthenium complexes alcohol oxidation, 788-9 alkene/alkyne vicinal dihydroxylation, 556 dioxetane decomposition, 1189-90... 

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